Stain repellent compositions and applications thereof

ABSTRACT

The present invention provides fluorinated compounds as well as dispersions of the fluorinated compounds. The fluorinated compounds described herein, in some embodiments, can be applied substrates such as textiles, including carpet and other floor coverings.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. patent application Ser. No.15/434,866, filed Feb. 16, 2017, which claims priority to U.S. patentapplication Ser. No. 12/719,376, filed Mar. 8, 2010, issued as U.S. Pat.No. 9,598,526, which claims priority pursuant to 35 U.S.C. § 119(e) toU.S. Provisional Patent Application Ser. No. 61/158,282, filed Mar. 6,2009 and U.S. Provisional Patent Application Ser. No. 61/223,109, filedJul. 6, 2009, all of which are hereby incorporated by reference in theirentirety.

FIELD OF THE INVENTION

The present invention relates to fluorinated compounds operable toimpart oil, water and/or soil repellency to substrates such as textilesincluding fabrics, carpets and other floor coverings.

BACKGROUND OF THE INVENTION

Manufactures of textiles are continuously searching for compositions toenhance textile fiber performance and durability. In the carpet andfloor coverings industry, for example, manufacturers desire compositionsoperable to render carpet fibers stain resistant. Fluorinated compoundshave been used extensively to impart water and oil repellency to textileand carpet fibers. Fluorocarbon compounds, for example, can provide bothoil and water repellency, unlike waxes, silicones, etc., which typicallyprovide water repellency, but are somewhat oleophilic, and thus do notprovide good oil repellency.

Fluorinated compounds, when applied to fibers in sufficient amount, canlower the surface energy of the fiber or fabric below the surface energyof water or oils that might be spilled onto the fabric, thereby allowingremoval of these liquids before penetration into the fiber or fabric.This is of great benefit for fibers and fabrics used in clothing,residential, commercial, and industrial settings as the useful life ofthe fibers and fabric is substantially increased.

The manufacture of fluorinated compounds, nevertheless, generallyemploys the use of organic solvents presenting several disadvantages.Substrates, including textile fibers, treated with organic solutions ordispersions of fluorinated compounds, for example, often require anextraction step to remove the organic solvent. An extraction stepincreases the time and cost of producing a stain repellent substrate.

Organic solvent extraction from a substrate can be avoided by usingaqueous dispersions of fluorinated compounds. However, production ofaqueous dispersions of fluorinated compounds necessitate stripping ofthe organic solvent used in the production of the fluorinated compounds.Organic solvent stripping from an aqueous dispersion by distillation andother techniques can additionally increase the time and cost ofproducing a stain repellent substrate. Furthermore, providing stableaqueous dispersions of fluorinated compounds can be difficult requiringthe use of dispersing aids such as surfactants and organic cosolvents.

SUMMARY

In view of the foregoing, the present invention provides fluorinatedcompounds as well as solutions and dispersions of the fluorinatedcompounds. In some embodiments, fluorinated compounds of the presentinvention are produced in the absence of an organic solvent orcosolvent. Moreover, in some embodiments, aqueous dispersions offluorinated compounds of the present invention do not comprisedispersing aids such as surfactants and/or organic cosolvents. In someembodiments, fluorinated compounds described herein and solutions ordispersions thereof can be applied substrates such as textiles,including carpet and other floor coverings.

In one aspect, the present invention provides a fluorinated compoundcomprising a reaction product of a polyisocyanate component and a diolcomponent or a diamine component or a mixture thereof, the reactionproduct further reacted with an organic component comprising moleculesof at least one compound having a plurality of fluorinated carbon atomsand at least one isocyanate reactive functionality. In some embodiments,the organic component further comprises molecules of at least onenon-fluorinated compound having at least one isocyanate reactivefunctionality.

In some embodiments, a fluorinated compound comprising a reactionproduct of a polyisocyanate component and a diol component or a diaminecomponent or a mixture thereof, the reaction product further reactedwith an organic component is a compound of Formula (I):

wherein Z is a trivalent organic group;L is a divalent diol, diamine, urea, dialcohol amine or an aminoalcoholor a mixture thereof;n ranges from 1 to 30;and A¹, A², A³ and A⁴ are independently selected from the groupconsisting of R^(f)—R^(a)—X— and R^(o)—X—, wherein at least one of A¹,A², A³ and A⁴ is R^(f)—R^(a)—X—;wherein R^(f) is a fluoroalkyl;R^(a) is a direct bond, alkyl, —C_(m)H_(2m)SO—, —C_(m)H_(2m)SO₂—,—SO₂N(R¹)—,—CON(R¹)—, wherein m ranges from 1 to 20 and R¹ is hydrogen or alkyl;andX is —O—, —S— or —N(R²)—, wherein R² is hydrogen or alkyl; andR^(o) is -alkyl, -alkenyl, -cycloalkyl, -chloroalkyl, -chloroalkenyl,-chlorocycloalkyl, —O-alkyl-glycidyl, —R³—O—R⁴,

or —O—R²⁴—O—C(O)—R²⁵,wherein R³, R⁴, R⁵, R⁶, R²⁴ and R²⁵ are independently selected from thegroup consisting of alkyl and alkenyl and p ranges from 1 to 50 andwherein the alkyl and alkenyl of R³-R⁶, R²⁴ and R²⁵ are optionallyindependently substituted one or more times with a substituent selectedfrom the group consisting of alkyl, alkenyl, and halo.

In some embodiments, A¹ is independently selected for each repeatingunit in Formula (I). In some embodiments of a compound of Formula (I),for example, A¹ is R^(f)—R^(a)—X— in one repeating unit and R^(o)—X— inanother repeating unit. Moreover, in some embodiments, A¹ is the same inall or substantially all of the repeating units of a compound of Formula(I).

In some embodiments, Z is selected from the following trivalent organiccompounds:

wherein R⁷, R⁸, R⁹, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² andR²³ are independently selected from the group consisting of alkyl,alkenyl, cycloalkyl, and aryl; and

wherein R¹⁰, R¹¹ and R¹² are independently selected from the groupconsisting of hydrogen and alkyl;

wherein the alkyl, alkenyl, cycloalkyl and aryl of groups of R⁷-R²³ areoptionally independently substituted one or more times with asubstituent selected from the group consisting of -alkyl, -alkenyl,-fluoroalkyl, -chloroalkyl, bromoalkyl, -aryl, —O-alkyl, —O— alkenyl,—O-aryl, —O-alkylene-aryl, -carboxyl, -hydroxyl,

-halo and -nitro; and

wherein

is a point of attachment of the trivalent organic compound in Formula(I).

Moreover, in some embodiments, L can comprise any divalent diol,diamine, urea, dialcohol amine or aminoalcohol not inconsistent with theprinciples and objectives of the present invention. In some embodimentsL is selected from the group consisting of ethylene glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, propylene glycol,dipropylene glycol, tripropylene glycol, 1,3-propanediol,1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,1,4-cylcohexanediol, ethanolamine, diethanolamine, methyldiethanolamineor phenyldiethanolamine, aminopropanol or mixtures thereof.

In some embodiments, fluoroalkyl, R^(f), is selected from the groupconsisting of C_(q)F_(2q+1) and (CF₃)₂CFO(CF₂CF₂)_(t) wherein q rangesfrom 4 to 20 and t ranges from 1 to 5. In one non-limiting embodiment,for example, q is 6.

Additionally, in some embodiments R^(o) is a monoalkyl ether of apolyalkylene glycol having the formula

as defined above. In some embodiments, R^(o) comprises a monoalkyl etherof a polyethylene glycol, polypropylene glycol or copolymers thereof. Insome embodiments, R^(o) comprises a chloroalkyl group.

Fluorinated compounds of the reaction products described herein,including fluorinated compounds of Formula (I), can have any desiredmolecular weight. The molecular weight of a fluorinated compound can beselected according to several parameters including the ability toprovide an aqueous dispersion of the fluorinated compound withoutdispersing agents and/or the ability to exhaust the fluorinated compoundonto a substrate.

In some embodiments, a fluorinated compound, including a compound ofFormula (I), comprising a reaction product of a polyisocyanate componentand a diol component or a diamine component or a mixture thereof, thereaction product further reacted with an organic component has amolecular weight of at least about 2,000. In some embodiments, afluorinated compound has a molecular weight of at least about 4,000. Insome embodiments, a fluorinated compound has a molecular weight greaterthan about 8,000. In one embodiment, for example, a fluorinated compoundhas a molecular weight ranging from about 8,250 to about 20,000. Inanother embodiment, a fluorinated compound has a molecular weightranging from about 9,000 to about 15,000. In some embodiments, afluorinated compound has a molecular weight less than about 2,000 orgreater than about 20,000.

In another aspect, the present invention provides aqueous dispersions ofa fluorinated compound comprising the reaction product of apolyisocyanate component and a diol component or a diamine component ora mixture thereof, the reaction product further reacted with an organiccomponent as described herein. In one embodiment, for example, thepresent invention provides aqueous dispersions of a compound of Formula(I). In some embodiments, aqueous dispersions of a fluorinated compoundare free or substantially free of dispersing aids including, but notlimited to, surfactants and/or organic cosolvents.

The present invention, in another aspect, provides a substrate at leastpartially treated or coated with a fluorinated compound comprising thereaction product of a polyisocyanate component and a diol component or adiamine component or a mixture thereof, the reaction product furtherreacted with an organic component as described herein. In someembodiments, a substrate is at least partially treated or coated with afluorinated compound of Formula (I). In some embodiments, a fluorinatedcompound is applied to substrate as an aqueous dispersion. In someembodiments, wherein an aqueous dispersion of a fluorinated compounddescribed herein does not comprise dispersing aids, a substrate treatedwith such a dispersion is not subjected to subsequent washing orextraction steps to remove residual dispersing aids.

Substrates, in some embodiments, comprise cellulosic materials,including paper, wood, cellulose acetate fibers, and cotton materials,including, but not limited to, cotton fibers, woven cotton articles, andnon-woven cotton articles. In other embodiments, a substrate comprisesother natural fibers including, but not limited to, wool and silkfibers.

In another embodiment, a substrate comprises synthetic fibers. Syntheticfibers, in some embodiments, comprise nylon (polyamide) fibers,polyester fibers such as PTT, polyethylene terephthalate (PET),polybutylene terephthalate (PBT), polyolefin fibers such aspolypropylene, polyurethane fibers, polyacrylonitrile fibers, orcombinations or composites thereof. In some embodiments, for example, asubstrate comprises a mixture or combination of synthetic fibersincluding PTT fibers combined with any one of polyester fibers such asPET and/or PBT fibers, polyamide fibers, polyolefin fibers such aspolypropylene fibers, polyurethane fibers, and/or any combinationthereof. In some embodiments, for example, a substrate comprises acombination of synthetic fibers including PTT fibers with naturalfibers. Substrates comprising various combinations of fibers, in someembodiments of the present invention, are considered compositesubstrates.

In a further embodiment, a substrate comprises leather, thermoplastics,thermosets, metals, porcelain, carpet, masonry, stones, brick, wood,plastics, painted surfaces, and dyed surfaces.

In coating or treating a substrate with an aqueous dispersion, afluorinated compound of the present invention, in some embodiments, isassociated with one or more surfaces of the substrate. In someembodiments, for example, a fluorinated compound is associated with asurface of the substrate through electrostatic interactions, covalentbonds, dipole-dipole interactions, van der Waals interactions orhydrophobic interactions or combinations thereof. In other embodiments,a fluorinated compound is associated with a surface of a substrate bymechanical engagement. In one embodiment, for example, a fluorinatedcompound described herein is trapped between a plurality of filaments ina fiber such as a synthetic fiber. In some embodiments, a fluorinatedcompound is trapped between polymeric chains of one or more fiberfilaments.

Fluorinated compounds of the present invention, in some embodiments, canbe applied with other stain resistant species. In some embodiments, asubstrate treated or coated with a fluorinated compound can demonstrateincreased or enhanced repellency of oil and water. Moreover, in someembodiments, a substrate treated or coated with a fluorinated compoundcan demonstrate advantageous soil resistance and/or release properties.

In another aspect, the present invention provides methods of producingfluorinated compounds. In one embodiment, a method of producing afluorinated compound comprises reacting a polyisocyanate component witha diol component or a diamine component or a mixture thereof to providea reaction product and reacting the reaction product with an organiccomponent comprising molecules of at least one compound having aplurality of fluorinated carbon atoms and at least one isocyanatereactive functionality. In some embodiments, the organic componentfurther comprises molecules of at least one non-fluorinated compoundhaving at least one isocyanate reactive functionality.

In some embodiments, a method of producing a fluorinated compound ofFormula (I), for example, comprises reacting an amount of a bifunctionalisocyanate compound of formula:

with an amount of a diol or diamine component of formula:H-L-Hto produce a reaction product of a compound of Formula (IA):

wherein Z and L are defined above.

In some embodiments, a diol of formula H-L-H is selected from the groupconsisting of ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, 1,4-cylcohexanediol or mixtures thereof. In someembodiments, a diol of formula H-L-H comprises one or more diols havinga polymeric structure including, but not limited to, polyalkyleneglycols such as polyethylene glycols, polypropylene glycols or mixturesthereof. In some embodiments, diols having a polymeric structurecomprise polyester-based diols, polycarbonate-based diols or mixturesthereof. A diol having a polymeric structure can have any desiredmolecular weight not inconsistent with the objectives of the presentinvention.

In some embodiments, a dialcohol amine of formula H-L-H isdiethanolamine, methyldiethanolamine or phenyldiethanolamine or mixturesthereof. In some embodiments, an aminoalcohol of formula H-L-H isaminopropanol or ethanolamine or a mixture thereof.

In some embodiments, a diamine of formula H-L-H comprises ethylenediamine, propylene diamine, butylene diamine or hexamethylene diamine ormixtures thereof. A diamine also encompasses diamine derivativesincluding, but not limited to, diamides such as urea.

In some embodiments, a reaction product of Formula (IA) can beoligomeric or polymeric.

Unreacted isocyanate groups of the reaction product of Formula (IA) areindependently reacted with an organic component comprising molecules ofcompounds selected from the group consisting of Formula (II) and Formula(III):R^(f)—R^(a)—X—H  (II)R^(o)—X—H  (III)such that all or substantially all of the unreacted isocyanate groups ofthe reaction product of Formula (IA) have been reacted resulting in acompound of Formula (I), wherein R^(f), R^(a), R^(o) and X are definedabove. As provided herein, in some embodiments, the unreacted isocyanategroup of each repeating unit of a reaction product of Formula (IA) canreact with a compound of Formula (II) or a compound of Formula (III). Asa result, in some embodiments, an unreacted isocyanate of one repeatingunit can react with a compound of Formula (II) while an unreactedisocyanate group on an adjacent repeating unit can react with a compoundof Formula (III). In other embodiments, unreacted isocyanate groups ofadjacent repeating units each react with a compound of Formula (II) oreach react with a compound of Formula (III).

In some embodiments, a compound of Formula (II) comprises a fluorinatedalcohol of the formula (C_(q)F_(2q+1))(CH₂)_(u)OH, wherein q ranges from4 to 20 and u ranges from 1 to 20. In one embodiment, for example, acompound of Formula (II) provided for reaction with unreacted isocyanategroups of a reaction product of Formula (IA) is a single species offluorinated alcohol. In some embodiments, a single species offluorinated alcohol is selected from the group consisting of(C₄F₉)(CH₂)_(u)OH, (C₆F₁₃)(CH₂)_(u)OH, (C₈F₁₇)(CH₂)_(u)OH,(C₁₀F₂₁)(CH₂)_(u)OH, (C₁₂F₂₅)(CH₂)_(u)OH, (C₁₄F₂₈)(CH₂)_(u)OH,(C₁₆F₃₃)(CH₂)_(u)OH, (C₁₈F₃₉)(CH₂)_(u)OH and (C₂₀F₄₁)(CH₂)_(u)OH whereinu is defined above.

In other embodiments, a compound of Formula (II) for reaction withunreacted isocyanate groups of a reaction product of Formula (IA) isprovided as a mixture fluoroalcohols. In some embodiments, a mixture cancomprise any two or more of the following fluoroalcohols:(C₄F₉)(CH₂)_(u)OH, (C₆F₁₃)(CH₂)_(u)OH, (C₈F₁₇)(CH₂)_(u)OH,(C₁₀F₂₁)(CH₂)_(u)OH, (C₁₂F₂₅)(CH₂)_(u)OH, (C₁₄F₂₈)(CH₂)_(u)OH,(C₁₆F₃₃)(CH₂)_(u)OH, (C₁₈F₃₉)(CH₂)_(u)OH and (C₂₀F₄₁)(CH₂)_(u)OH,wherein u is defined above.

Moreover, in some embodiments, a compound of Formula (III) comprises amonoalkyl ether of a polyalkylene glycol having the formula

as defined above. In some embodiments, a compound of Formula (III)provided for reaction with unreacted isocyanate groups of a reactionproduct of Formula (IA) is a single species of a monoalkyl ether of apolyalkylene glycol. In other embodiments, a compound of Formula (III)provided for reaction with unreacted isocyanate groups of a reactionproduct of Formula (IA) is provided as a mixture of various monoalkylethers of polyalkylene glycols.

In some embodiments, a compound of Formula (III) comprises a chlorinatedalcohol. Non-limiting examples of chlorinated alcohols comprise1,3-dichloro-2-propanol, 2,2,2-trichloroethanol and 2,2-dichloroethanol.

Moreover, a compound of Formula (III), in some embodiments, comprisesepoxy or glycidyl alcohols. A non-limiting example of an epoxy alcoholis 2,3-epoxy-1-propanol. In some embodiments, a compound of Formula(III) comprises hydroxy functional acrylates and methacrylatesincluding, but not limited to, 2-hydroxyethylmethacrylate,2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate and2-hydroxypropylacrylate.

In some embodiments, a compound of Formula (III) provided for reactionwith unreacted isocyanate groups of a reaction product of Formula (IA)comprises a mixture comprising at least two of polyalkylene glycol, achlorinated alcohol, a glycidyl alcohol and a hydroxy functionalacrylate.

As provided herein, methods of producing fluorinated compounds, in someembodiments, do not employ organic solvents.

In another aspect, the present invention provides a method of producingan aqueous dispersion of a fluorinated compound comprising the reactionproduct of a polyisocyanate component and a diol component or a diaminecomponent or a mixture thereof, the reaction product further reactedwith an organic component comprising molecules of at least one compoundhaving a plurality of fluorinated carbon atoms and at least oneisocyanate reactive functionality. In one embodiment, a method ofproducing a dispersion of a fluorinated compound described hereincomprises providing the fluorinated compound and dispersing thefluorinated compound in an aqueous medium without the use of adispersing aid. Fluorinated compounds can be provided according to themethods of synthesis described herein.

Production of fluorinated compounds described herein in the absence oforganic solvents, in some embodiments, can facilitate the production ofaqueous dispersions of the fluorinated compounds. The absence of anorganic solvent, for example, can preclude the requirement to strip orfurther process the organic solvent during production of the aqueousdispersion. As a result, in some embodiments, water can be addeddirectly to the reaction mixture comprising a fluorinated compound toproduce an aqueous dispersion of the fluorinated compound.

In a further aspect, the present provides methods of enhancing the oiland/or water repellency of substrates, including fibers, textiles,carpets and floor coverings. In one embodiment, a method of enhancingthe oil and/or water repellency of a substrate comprises providing anaqueous dispersion of a fluorinated compound described herein andapplying the aqueous dispersion to the substrate.

In some embodiments, applying the aqueous dispersion to the substratecomprises spray coating, dip coating, foaming, exhausting, passing thesubstrate through kiss rollers or spreading onto or coating thesubstrate through a head box, optionally with the aid of a doctor bladeor any other application or exhaustion method or technique known to oneof skill in the art.

These and other embodiments are described in greater detail in thedetailed description which follows.

DETAILED DESCRIPTION

The term “alkyl” as used herein, alone or in combination, refers to astraight or branched chain saturated hydrocarbon radical having from 1to 20 carbon atoms. Non-limiting examples of alkyl groups includeC₁₋₈-alkyl or C₁₋₆-alkyl. Typical C₁₋₈-alkyl groups and C₁₋₆-alkylgroups include, but are not limited to e.g. methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl,2-methylbutyl, 3-methylbutyl, 4-methylpentyl, neopentyl, n-pentyl,n-hexyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyland the like. The term “C₁₋₈-alkyl” as used herein also includessecondary C₃₋₈-alkyl and tertiary C₄₋₈-alkyl. The term “C₁₋₆-alkyl” asused herein also includes secondary C₃₋₆-alkyl and tertiary C₄₋₆-alkyl.

The term “alkenyl” as used herein, alone or in combination, refers to astraight or branched chain hydrocarbon radical containing from 2 to 20carbon atoms and at least one carbon-carbon double bond. Non-limitingexamples of alkenyl groups include C₂₋₈-alkenyl or C₂₋₆-alkenyl. TypicalC₂₋₈-alkenyl groups and C₂₋₆-alkenyl groups include, but are not limitedto, vinyl, 1-propenyl, 2-propenyl, iso-propenyl, 1,3-butadienyl,1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 1-pentenyl,2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-hexenyl,2-hexenyl, 3-hexenyl, 2,4-hexadienyl, 5-hexenyl and the like.

The term “cycloalkyl” as used herein, alone or in combination, refers toa non-aromatic hydrocarbon radical having from three to twelve carbonatoms, and optionally with one or more degrees of unsaturation, forexample C₃₋₈-cycloalkyl. Such a ring may be optionally fused to one ormore benzene rings or to one or more of other cycloalkyl ring(s).Typical C₃₋₈-cycloalkyl groups include, but are not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl,cycloheptyl, cycloheptenyl, cyclooctyl and the like.

The term “aryl” as used herein refers to a carbocyclic aromatic ringradical or to a aromatic ring system radical. Aryl is also intended toinclude the partially hydrogenated derivatives of the carbocyclicsystems.

The term “fluoroalkyl,” as used herein, has the same respective meaningsas alkyl and alkenyl above provided that at least one carbon atom of thegroup is substituted with at least one fluorine atom. In someembodiments, more than one carbon atom of the alkyl group is substitutedwith a plurality fluorine atoms. Fluoroalkyl additionally encompassesperfluorinated alkyl and alkenyl groups.

The term “chloroalkyl,” as used herein, has the same respective meaningsas alkyl and alkenyl above provided that at least one carbon atom of thegroup is substituted with at least one chlorine atom. In someembodiments, more than one carbon atom of the alkyl group is substitutedwith a plurality chlorine atoms. Chloroalkyl additionally encompassesperchlorinated alkyl and alkenyl groups.

The term “isocyanate reactive functionality,” as used herein, refers toa chemical functionality capable of chemically reacting with anisocyanate group. Non-limiting examples of a isocyanate reactivefunctionality include hydroxyl, carboxyl, amine, thiol and several otherfunctional groups containing an active hydrogen moiety.

The present invention provides fluorinated compounds as well assolutions and dispersions of the fluorinated compounds. In someembodiments, fluorinated compounds described herein are produced in theabsence of an organic solvent. Moreover, in some embodiments, aqueousdispersions of fluorinated compounds of the present invention do notcomprise dispersing aids such as surfactants and/or organic cosolvents.Fluorinated compounds described herein and solutions or dispersionsthereof can be applied substrates such as textiles, including carpet andother floor coverings.

In one aspect, the present invention provides a fluorinated compoundcomprising a reaction product of a polyisocyanate component and a diolcomponent or a diamine component or a mixture thereof, the reactionproduct further reacted with an organic component comprising moleculesof at least one compound having a plurality of fluorinated carbon atomsand at least one isocyanate reactive functionality. In some embodiments,the organic component further comprises molecules of at least onenon-fluorinated compound having at least one isocyanate reactivefunctionality.

A polyisocyanate component used in the production of the reactionproduct can comprise molecules of one or more species ofpolyisocyanates. In some embodiments, a polyisocyanate componentcomprises molecules having at least three isocyanate groups. In someembodiments a polyisocyanate component comprises molecules having atleast four or at least five isocyanate groups. In some embodiments, apolyisocyanate component comprises molecules of one or more of thefollowing polyisocyanates:

wherein R⁷, R⁸, R⁹, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² andR²³ are independently selected from the group consisting of alkyl,alkenyl, cycloalkyl, and aryl; and

wherein R¹⁰, R¹¹ and R¹² are independently selected from the groupconsisting of hydrogen and alkyl; and

wherein the alkyl, alkenyl, cycloalkyl and aryl of groups of R⁷-R²³ areoptionally independently substituted one or more times with asubstituent selected from the group consisting of -alkyl, -alkenyl,-fluoroalkyl, -chloroalkyl, -bromoalkyl, -aryl, —O-alkyl, —O-alkenyl,—O-aryl, —O-alkylene-aryl, -carboxyl, -hydroxyl,

-halo and -nitro.

In some embodiments, suitable polyisocyanates are commercially availablefrom Bayer Material Science of Pittsburgh, Pa. under the DESMODUR® tradedesignation including, but not limited to, DESMODUR® N-3300A, DESMODUR®N-3200, DESMODUR® N-3400, DESMODUR® N-3600 and DESMODUR® XP 2410. Insome embodiments, suitable polyisocyanates are commercially availablefrom Bayer Material Science of Pittsburgh, Pa. under the BAYHYDUR® tradedesignation including, but not limited to, BAYHYDUR® XP 2547. In someembodiments, suitable polyisocyanates are commercially available fromPerstorp of Toledo, Ohio under the TOLONATE® trade designationincluding, but not limited to, TOLONATE® HDT, TOLONATE® HDT-LV,TOLONATE® HDT-LV2, TOLONATE® HDB and TOLONATE® HDB-LV.

A diol component, which in some embodiments is used in conjunction withthe polyisocyanate component in the production of a reaction product,can comprise molecules of one or more species of diols. In someembodiments, a diol component comprises molecules of ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol,1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,1,4-cylcohexanediol, diethanolamine, methyldiethanolamine orphenyldiethanolamine or mixtures thereof.

In some embodiments, a diol component comprises one or more diols havinga polymeric structure including, but not limited to, polyalkyleneglycols such as polyethylene glycols, polypropylene glycols or mixturesthereof. In some embodiments, diols having a polymeric structurecomprise ethylene oxide/propylene oxide copolymers. In some embodiments,diols having a polymeric structure comprise polyester-based diols,polycarbonate-based diols or mixtures thereof. A diol having a polymericstructure can have any desired molecular weight not inconsistent withthe objectives of the present invention. In some embodiments, a diolcomponent comprises polyethylene glycol (PEG) 300, PEG 400, PEG 600 ormixtures thereof. In some embodiments, a diol component comprisespolypropylene glycol (PPG) 1000, PPG 2000 or mixtures thereof. In someembodiments, a diol component comprises a PEG and/or PPG that is liquidat room temperature.

A diamine component, which in some embodiments is used in conjunctionwith the polyisocyanate component in the production of a reactionproduct, can comprise molecules of one or more species of diamines.Amine functionalities of diamines suitable for use in the diaminecomponent comprise at least one hydrogen operable for reaction with anisocyanate functionality. In some embodiments, a diamine componentcomprises molecules of ethylene diamine, propylene diamine, butylenediamine or hexamethylene diamine or mixtures thereof. A diaminecomponent also encompasses diamine derivatives including, but notlimited to, diamides such as urea. A diamine component also encompassesmonoalcohol amines such as ethanolamine, aminopropanol or mixturesthereof. In some embodiments, a fluorinated compound described hereindoes not comprise a urea linkage.

As described herein, the polyisocyanate component is reacted with thediol component or the diamine component or a mixture thereof to providea reaction product. The reaction product is subsequently reacted with anorganic component comprising molecules of at least one compound having aplurality of fluorinated carbon atoms and at least one isocyanatereactive functionality.

In some embodiments, a compound of an organic component having aplurality of fluorinated carbon atoms and at least one isocyanatereactive functionality is a compound of Formula (II):R^(f)—R^(a)—X—H  (II)wherein R^(f), R^(a), R^(o) and X are defined above. In someembodiments, a compound of Formula (II) comprises a fluorinated alcoholof the formula (C_(q)F_(2q+1))(CH₂)_(u)OH, wherein q ranges from 4 to 20and u ranges from 1 to 20. In some embodiments, for example, moleculesof a compound of Formula (II) react with unreacted isocyanate groups ofthe reaction product resulting from the combination of thepolyisocyanate component with the diol component and/or diaminecomponent. In some embodiments, a single species of fluorinated alcoholis selected from the group consisting of (C₄F₉)(CH₂)_(u)OH,(C₆F₁₃)(CH₂)_(u)OH, (C₈F₁₇)(CH₂)_(u)OH, (C₁₀F₂₁)(CH₂)_(u)OH,(C₁₂F₂₅)(CH₂)_(u)OH, (C₁₄F₂₈)(CH₂)_(u)OH, (C₁₆F₃₃)(CH₂)_(u)OH,(C₁₈F₃₉)(CH₂)_(u)OH and (C₂₀F₄₁)(CH₂)_(u)OH wherein u is defined above.

In other embodiments, a compound of Formula (II) is provided as amixture fluoroalcohols. In some embodiments, a mixture can comprise anytwo or more of the following fluoroalcohols: (C₄F₉)(CH₂)_(u)OH,(C₆F₁₃)(CH₂)_(u)OH, (C₈F₁₇)(CH₂)_(u)OH, (C₁₀F₂₁)(CH₂)_(u)OH,(C₁₂F₂₅)(CH₂)_(u)OH, (C₁₄F₂₈)(CH₂)_(u)OH, (C₁₆F₃₃)(CH₂)_(u)OH,(C₁₈F₃₉)(CH₂)_(u)OH and (C₂₀F₄₁)(CH₂)_(u)OH, wherein u is defined above.

In some embodiments, the organic component further comprises moleculesof at least one non-fluorinated compound having at least one isocyanatereactive functionality. In some embodiments, a non-fluorinated compoundhaving at least one isocyanate reactive functionality is a compound ofFormula (III):R^(o)—X—H  (III)wherein R^(o) and X are defined above. In some embodiments, a compoundof Formula (III) comprises one or more monoalkyl ethers of apolyalkylene glycol having the formula

as defined above. In some embodiments, for example, molecules of acompound of Formula (III) react with unreacted isocyanate groups of thereaction product resulting from the combination of the polyisocyanatecomponent with the diol component and/or diamine component.

In some embodiments, a compound of Formula (III) comprises a chlorinatedalcohol. Non-limiting examples of chlorinated alcohols comprise1,3-dichloro-2-propanol, 2,2,2-trichloroethanol and 2,2-dichloroethanol.

Moreover, a compound of Formula (III), in some embodiments, comprisesepoxy or glycidyl alcohols. A non-limiting example of an epoxy alcoholis 2,3-epoxy-1-propanol. In some embodiments, a compound of Formula(III) comprises hydroxy functional acrylates and methacrylatesincluding, but not limited to, 2-hydroxyethylmethacrylate,2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate and2-hydroxypropylacrylate.

In some embodiments, a fluorinated compound comprising a reactionproduct of a polyisocyanate component and a diol component or a diaminecomponent or a mixture thereof, the reaction product further reactedwith an organic component is a compound of Formula (I):

wherein Z is a trivalent organic group;L is a divalent diol, diamine, urea, dialcohol amine or an aminoalcoholor a mixture thereof;n ranges from 1 to 30;and A¹, A², A³ and A⁴ are independently selected from the groupconsisting of R^(f)—R^(a)—X— and R^(o)—X—, wherein at least one of A¹,A², A³ and A⁴ is R^(f)—R^(a)—X—;wherein R^(f) is a fluoroalkyl;R^(a) is a direct bond, alkyl, —C_(m)H_(2m)SO—, —C_(m)H_(2m)SO₂—,—SO₂N(R¹)—,—CON(R¹)—, wherein m ranges from 1 to 20 and R¹ is hydrogen or alkyl;andX is —O—, —S— or —N(R²)—, wherein R² is hydrogen or alkyl; andR^(o) is -alkyl, -alkenyl, -cycloalkyl, -chloroalkyl, -chloroalkenyl,-chlorocycloalkyl, —O-alkyl-glycidyl, —R³—O—R⁴,

or —O—R²⁴—O—C(O)—R²⁵,wherein R³, R⁴, R⁵, R⁶, R²⁴ and R²⁵ are independently selected from thegroup consisting of alkyl and alkenyl and p ranges from 1 to 50 andwherein the alkyl and alkenyl of R³-R⁶, R²⁴ and R²⁵ are optionallyindependently substituted one or more times with a substituent selectedfrom the group consisting of alkyl, alkenyl, and halo.

In some embodiments, A¹ is independently selected for each repeatingunit in Formula (I). In some embodiments of a compound of Formula (I),for example, A¹ is R^(f)—R^(a)—X— in one repeating unit and R^(o)—X— inanother repeating unit. Moreover, in some embodiments, A¹ is the same inall or substantially all of the repeating units of a compound of Formula(I).

In some embodiments, Z is selected from the following trivalent organiccompounds:

wherein R⁷, R⁸, R⁹, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² andR²³ are independently selected from the group consisting of alkyl,alkenyl, cycloalkyl, and aryl; and

wherein R¹⁰, R¹¹ and R¹² are independently selected from the groupconsisting of hydrogen and alkyl;

wherein the alkyl, alkenyl, cycloalkyl and aryl of groups of R⁷-R²³ areoptionally independently substituted one or more times with asubstituent selected from the group consisting of -alkyl, -alkenyl,-fluoroalkyl, -chloroalkyl, bromoalkyl, -aryl, —O-alkyl, —O-alkenyl,—O-aryl, —O-alkylene-aryl, -carboxyl, -hydroxyl,

-halo and -nitro; and

wherein

is a point of attachment of the trivalent organic compound in Formula(I).

Additionally, in some embodiments R^(o) is a monoalkyl ether of apolyalkylene glycol having the formula

as defined above. In some embodiments, R^(o) comprises a monoalkyletherof a polyethylene glycol, polypropylene glycol or copolymers thereof.

Non-limiting examples of a compounds of Formula (I) are as follows:

wherein A¹, A², A³ and A⁴ are independently selected from the groupconsisting of (C₆F₁₃)(CH₂)₆O— and

and n is defined above. As described herein, it is important to notethat identity of A¹ can be independently selected for each repeatinggroup in the foregoing non-limiting examples. In one embodiment,example, A¹ of one repeating unit is a flourocompound of formula(C₆F₁₃)(CH₂)₆O— while A¹ of another repeating unit is a methyl ether ofpolyethylene glycol of the formula:

In some embodiments, at least one of A¹ through A⁴ comprises achloroalkyl group. As discussed further herein, in some embodiments,chloroalkyl groups can be provided as chloroalcohols in the synthesis ofcompounds of Formula (I). In some embodiments, chloroalkyl groups canenhance the resistance to flammability of dispersions and/or substratescomprising compounds of Formula (I).

In some embodiments, a fluorinated compound, including a compound ofFormula (I), comprising a reaction product of a polyisocyanate componentand a diol component or a diamine component or a mixture thereof, thereaction product further reacted with an organic component has amolecular weight of at least about 2,000. In some embodiments, afluorinated compound has a molecular weight of at least about 4,000. Insome embodiments, a fluorinated compound has a molecular weight greaterthan about 8,000. In one embodiment, for example, a fluorinated compoundhas a molecular weight ranging from about 8,250 to about 20,000. Inanother embodiment, a fluorinated compound has a molecular weightranging from about 9,000 to about 15,000. In some embodiments, afluorinated compound has a molecular weight less than about 2,000 orgreater than about 20,000.

In some embodiments, the molecular weight of a fluorinated compound,such as a compound of Formula (I), can be controlled based on the amountof chain extender (e.g., diol, diamine, urea, dialcohol amine oraminoalcohol) used in producing the compound. Lower amounts of chainextender, for example, can produce fluorinated compounds having lowermolecular weights while higher amounts of chain extender can producefluorinated compounds having higher molecular weights. Moreover, in someembodiments, the molecular weight of fluorinated compounds describedherein can be controlled based on the identity of a polyglycol used inthe synthesis of the compounds. Higher molecular weight polyglycols, insome embodiments, can provide fluorinated compounds with highermolecular weight.

In another aspect, the present invention provides an aqueous dispersionof a fluorinated compound comprising the reaction product of apolyisocyanate component and a diol component or a diamine component ora mixture thereof, the reaction product further reacted with an organiccomponent as described herein. In some embodiments, aqueous dispersionsof fluorinated compounds described herein are free or substantially freeof dispersing aids including, but not limited to, surfactants,emulsifiers and/or organic cosolvents.

In some embodiments, an aqueous dispersion comprises particles of afluorinated compound described herein having an average size rangingfrom about 1 nm to about 500 nm. In other embodiments, an aqueousdispersion comprises particles of a fluorinated compound having anaverage size ranging from about 10 nm to about 400 nm or from about 50nm to about 300 nm. In another embodiment, an aqueous dispersioncomprises particles of a fluorinated compound described having anaverage size ranging from about 100 nm to about 250 nm. In someembodiments, an aqueous dispersion comprises particles of a fluorinatedcompound having an average size ranging from about 10 nm to about 120 nmor from about 20 nm to about 100 nm. In a further embodiment, an aqueousdispersion comprises particles of a fluorinated compound having anaverage size less than about 1 nm or greater than about 500 nm.

An aqueous dispersion can comprise any desired amount of a fluorinatedcompound. In some embodiments, an aqueous dispersion comprises particlesof a fluorinated compound described herein in an amount ranging fromabout 0.01 weight percent to about 30 weight percent. In someembodiments an aqueous dispersion comprises particles of a fluorinatedcompound in an amount ranging from about 1 weight percent to about 25weight percent. In another embodiment, an aqueous dispersion comprisesparticles of a fluorinated compound in an amount ranging from about 5weight percent to about 20 weight percent. In some embodiments, anaqueous dispersion comprises particles of a fluorinated compound in anamount ranging from about 10 weight percent to about 15 weight percent.In a further embodiment, an aqueous dispersion of the present inventioncomprises particles of a fluorinated compound in an amount less thanabout 0.01 weight percent or in an amount greater than about 30 weightpercent.

In some embodiments, an aqueous dispersion can further comprise otherfluorochemical species dispersed in the aqueous phase in addition to afluorinated compound described herein. Additional fluorochemicalspecies, in some embodiments, comprise fluoroalkyl methacrylates,fluoroalkyl acrylates, fluoroalkyl aryl urethanes, fluoroalkylurethanes, aliphatic fluoroalkyl urethanes, fluoroalkyl allyl urethanes,fluoroalkyl urethane acrylates, fluoroalkyl acrylamides, or fluoroalkylsulfonamide acrylates or mixtures thereof. In some embodiments,additional fluorochemical species comprise polytetrafluoroethylene(PTFE), fluorinated ethylene-propylene (FEP), perfluoroalkoxy resin(PFA), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene(EPTFE), polyvinylidene fluoride (PVDF), or polyvinyl fluoride (PVF) ormixtures thereof. Additional fluorochemical species, in someembodiments, can have particle sizes consistent with the particles sizesrecited for fluorinated compounds described herein.

The present invention, in another aspect, provides a substrate at leastpartially treated or coated with a fluorinated compound describedherein, including, but not limited to, a compound of Formula (I). Insome embodiments, a fluorinated compound is applied to substrate as anaqueous dispersion. In some embodiments, wherein an aqueous dispersionof a fluorinated compound does not comprise dispersing aids, a substratetreated with such a dispersion is not subjected to subsequent washing orextraction steps to remove residual dispersing aids.

Substrates, in some embodiments, comprise cellulosic materials,including paper, wood, cellulose acetate fibers, and cotton materials,including, but not limited to, cotton fibers, woven cotton articles, andnon-woven cotton articles. In other embodiments, a substrate comprisesother natural fibers including, but not limited to, wool and silkfibers.

In some embodiments, a substrate comprises synthetic fibers. Syntheticfibers, in some embodiments, comprise nylon (polyamide) fibers,polyester fibers such as PTT, polyethylene terephthalate (PET),polybutylene terephthalate (PBT), polyolefin fibers such aspolypropylene, polyurethane fibers, polyacrylonitrile fibers, orcombinations or composites thereof. In some embodiments, for example, asubstrate comprises a mixture or combination of synthetic fibersincluding PTT fibers combined with any one of polyester fibers such asPET and/or PBT fibers, polyamide fibers, polyolefin fibers such aspolypropylene fibers, polyurethane fibers, and/or any combinationthereof. In some embodiments, for example, a substrate comprises acombination of synthetic fibers, including PTT fibers, with naturalfibers. Substrates comprising various combinations of fibers, in someembodiments of the present invention, are considered compositesubstrates.

In a further embodiment, a substrate comprises leather, thermoplastics,thermosets, metals, porcelain, carpet, masonry, stones, brick, wood,plastics, painted surfaces, and dyed surfaces.

In coating or treating a substrate with an aqueous dispersion, afluorinated compound described herein, in some embodiments, isassociated with one or more surfaces of the substrate. In someembodiments, a fluorinated compound is associated with a surface of thesubstrate through electrostatic interactions, covalent bonds,dipole-dipole interactions, van der Waals interactions or hydrophobicinteractions or combinations thereof. In other embodiments, afluorinated compound is associated with a surface of a substrate bymechanical engagement. In one embodiment, for example, a fluorinatedcompound is trapped between a plurality of filaments in a fiber such asa synthetic fiber.

In some embodiments, a substrate treated or coated with a fluorinatedcompound described herein can demonstrate increased repellency of oiland water. Moreover, in some embodiments, a substrate treated or coatedwith a fluorinated compound can demonstrate advantageous soil resistanceand/or release properties.

In some embodiments, a substrate treated with an aqueous dispersion of afluorinated compound described herein has an oil repellency of at least5 according to the American Association of Textile Chemists andColorists (AATCC) Test Method 118. In other embodiments, a substratetreated with an aqueous dispersion of a fluorinated compound has an oilrepellency of at least 6 according to AATCC 118.

In some embodiments, aqueous dispersion of the present invention can beapplied to a substrate by spray coating, dip coating, foaming,exhausting, passing the substrate through kiss rollers or spreading ontoor coating the substrate through a head box, optionally with the aid ofa doctor blade or any other application or exhaustion method ortechnique known to one of skill in the art.

Moreover, in some embodiments, a substrate treated with an aqueousdispersion of a fluorinated compound described herein can be furthertreated with an additional fluorochemical species including, but notlimited to, fluoroalkyl methacrylates, fluoroalkyl acrylates,fluoroalkyl aryl urethanes, fluoroalkyl urethanes, aliphatic fluoroalkylurethanes, fluoroalkyl allyl urethanes, fluoroalkyl urethane acrylates,fluoroalkyl acrylamides, or fluoroalkyl sulfonamide acrylates ormixtures thereof. In other embodiments, polymeric particles comprisepolytetrafluoroethylene (PTFE), fluorinated ethylene-propylene (FEP),perfluoroalkoxy resin (PFA), polychlorotrifluoroethylene (PCTFE),ethylene-tetrafluoroethylene (EPTFE), polyvinylidene fluoride (PVDF), orpolyvinyl fluoride (PVF) or mixtures thereof.

In some embodiments, the additional fluorochemical species is acomponent of the aqueous dispersion of a fluorinated compound describedherein. In other embodiments, the additional fluorochemical is not acomponent of an aqueous dispersion of a fluorinated compound describedherein and is applied as a separate and independent composition to asubstrate.

In another aspect, the present invention provides methods of producingfluorinated compounds. In one embodiment, a method of producing afluorinated compound comprises reacting a polyisocyanate component witha diol component or a diamine component or a mixture thereof to providea reaction product and reacting the reaction product with an organiccomponent comprising molecules of at least one compound having aplurality of fluorinated carbon atoms and at least one isocyanatereactive functionality. In some embodiments, the organic componentfurther comprises molecules of at least one non-fluorinated compoundhaving at least one isocyanate reactive functionality.

In some embodiments, a method of producing a fluorinated compound ofFormula (I) comprises reacting an amount of a trifunctional isocyanatecompound of formula:

with an amount of a diol, diamine, urea, dialcohol amine, or anaminoalcohol or a mixture thereof of formula:H-L-Hto produce a reaction product of Formula (IA):

wherein Z and L are defined above.

In some embodiments, a diol of formula H-L-H is selected from the groupconsisting of ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, 1,4-cylcohexanediol or mixtures thereof. In someembodiments, a diol of formula H-L-H comprises one or more diols havinga polymeric structure including, but not limited to, polyalkyleneglycols such as polyethylene glycols, polypropylene glycols or mixturesthereof. In some embodiments, diols having a polymeric structurecomprise polyester-based diols, polycarbonate-based diols or mixturesthereof. A diol having a polymeric structure can have any desiredmolecular weight not inconsistent with the objectives of the presentinvention.

In some embodiments, a dialcohol amine of formula H-L-H isdiethanolamine, methyldiethanolamine or phenyldiethanolamine or mixturesthereof. In some embodiments, an aminoalcohol of formula H-L-H isaminopropanol or ethanolamine or a mixture thereof.

In some embodiments, a diamine of formula H-L-H comprises ethylenediamine, propylene diamine, butylene diamine or hexamethylene diamine ormixtures thereof. A diamine also encompasses diamine derivativesincluding, but not limited to, diamides such as urea.

Moreover, in some embodiments, trifunctional isocyanate compounds can beobtained from Bayer Material Science of Pittsburgh, Pa. under theDESMODUR® trade designation.

In some embodiments, a reaction product of Formula (IA) can beoligomeric or polymeric. Trifunctional isocyanate and diol and/ordiamine can be provided in any desired amount or ratio to produce areaction product of Formula (IA). As provided herein, increased amountsof diol and/or diamine can increase the molecular weight of a reactionproduct of Formula (IA) which concomitantly increases the molecularweight of a fluorinated compound of Formula (I).

In some embodiments, trifunctional isocyanate and diol can be reacted inthe presence of a catalyst, such as dibutyltin dilaurate, in a reactionvessel under nitrogen, with agitation and at a temperature ranging fromabout 65° C. to about 105° C. for a period of two hours to produce areaction product of Formula (IA).

Unreacted isocyanate groups of a reaction product of Formula (IA) areindependently reacted with a compound selected from the groupsconsisting of Formula (II) and Formula (III):R^(f)—R^(a)—X—H  (II)R^(o)—X—H  (III)such that all or substantially all of the unreacted isocyanate groups ofthe reaction product of Formula (IA) have been reacted resulting in acompound of Formula (I), wherein R^(f), R^(a), R^(o) and X are definedabove. As provided herein, in some embodiments, an unreacted isocyanategroup of each repeating unit of a reaction product of Formula (IA) canreact with a compound of Formula (II) or a compound of Formula (III). Asa result, in some embodiments, an unreacted isocyanate of one repeatingunit can react with a compound of Formula (II) while an unreactedisocyanate group on an adjacent repeating unit can react with a compoundof Formula (III). In other embodiments, unreacted isocyanate groups ofadjacent repeating units each react with a compound of Formula (II) oreach react with a compound of Formula (III).

Independently reacting unreacted isocyanate groups with a compoundselected from the group consisting of Formula (II) and Formula (III), insome embodiments, can be achieved by adding compounds of Formula (II)and Formula (III) to a reaction vessel comprising a reaction product ofFormula (IA). Once added, the reaction mixture can be held above 95° C.for a period of two hours resulting in the production of a fluorinatedcompound of Formula (I).

In some embodiments, a compound of Formula (II) comprises a fluorinatedalcohol of the formula (C_(q)F_(2q+1))(CH₂)_(u)OH, wherein q ranges from4 to 20 and u ranges from 1 to 20. In one embodiment, for example, acompound of Formula (II) provided for reaction with unreacted isocyanategroups of a reaction product of Formula (IA) is a single species offluorinated alcohol. In some embodiments, a single species offluorinated alcohol is selected from the group consisting of(C₄F₉)(CH₂)_(u)OH, (C₆F₁₃)(CH₂)_(u)OH, (C₈F₁₇)(CH₂)_(u)OH,(C₁₀F₂₁)(CH₂)_(u)OH, (C₁₂F₂₅)(CH₂)_(u)OH, (C₁₄F₂₈)(CH₂)_(u)OH,(C₁₆F₃₃)(CH₂)_(u)OH, (C₁₈F₃₉)(CH₂)_(u)OH and (C₂₀F₄₁)(CH₂)_(u)OH,wherein u is defined above. In other embodiments, a compound of Formula(II) provided for reaction with unreacted isocyanate groups of areaction product of Formula (IA) comprises a mixture fluoroalcohols. Insome embodiments, a mixture can comprise any two or more of thefollowing fluoroalcohols: (C₄F₉)(CH₂)_(u)OH, (C₆F₁₃)(CH₂)_(u)OH,(C₈F₁₇)(CH₂)_(u)OH, (C₁₀F₂₁)(CH₂)_(u)OH, (C₁₂F₂₅)(CH₂)_(u)OH,(C₁₄F₂₈)(CH₂)_(u)OH, (C₁₆F₃₃)(CH₂)_(u)OH, (C₁₈F₃₉)(CH₂)_(u)OH and(C₂₀F₄₁)(CH₂)_(u)OH, wherein u is defined above.

Moreover, in some embodiments, a compound of Formula (III) comprises amonoalkyl ether of a polyalkylene glycol having the formula

as defined above. In some embodiments, a compound of Formula (III)provided for reaction with unreacted isocyanate groups of a reactionproduct of Formula (IA) is a single species of a monoalkyl ether of apolyalkylene glycol. In other embodiments, a compound of Formula (III)provided for reaction with unreacted isocyanate groups of a reactionproduct of Formula (IA) comprises a mixture of various monoalkyl ethersof polyalkylene glycols.

Any monoalkyl ether of a polyalkylene glycol not inconsistent with theobjectives of the present invention can be used for reaction withunreacted isocyanate groups of a reaction product of Formula (IA) in theproduction of a fluorinated compound of Formula (I). In someembodiments, monoalkyl ether polyalkylene glycols are selected based onthe desired molecular weight of a fluorinated compound of Formula (I).In some embodiments, monoalkylether polyalkylene glycols comprisemethoxypolyethylene glycols (MPEG) such as MPEG 350, MPEG 550, MPEG 750,MPEG 1000 or MPEG 1450 or mixtures thereof. In some embodiments,monoalkylether polyalkylene glycols comprise methoxypropylene glycols.In another embodiment, monoalkylether polyalkylene glycols comprisepolyethylene and polypropylene glycol copolymers.

In some embodiments, a compound of Formula (III) comprises a chlorinatedalcohol. Non-limiting examples of chlorinated alcohols comprise1,3-dichloro-2-propanol, 2,2,2-trichloroethanol and 2,2-dichloroethanol.

Moreover, a compound of Formula (III), in some embodiments, comprisesepoxy or glycidyl alcohols. A non-limiting example of an epoxy alcoholis 2,3-epoxy-1-propanol. In some embodiments, a compound of Formula(III) comprises hydroxy functional acrylates and methacrylatesincluding, but not limited to, 2-hydroxyethylmethacrylate,2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate and2-hydroxypropylacrylate.

In some embodiments, a compound of Formula (III) provided for reactionwith unreacted isocyanate groups of a reaction product of Formula (IA)comprises a mixture comprising at least two of polyalkylene glycol, achlorinated alcohol, a glycidyl alcohol and a hydroxy functionalacrylate.

As provided herein, methods of producing fluorinated compounds, in someembodiments, do not employ organic solvents.

In another aspect, the present invention provides a method of producingan aqueous dispersion of a fluorinated compound comprising the reactionproduct of a polyisocyanate component and a diol component or a diaminecomponent or a mixture thereof, the reaction product further reactedwith an organic component comprising molecules of at least one compoundhaving a plurality of fluorinated carbon atoms and at least oneisocyanate reactive functionality. In one embodiment, a method ofproducing a dispersion of a fluorinated compound described hereincomprises providing the fluorinated compound and dispersing thefluorinated compound in an aqueous medium without the use of adispersing aid. Fluorinated compounds can be provided according to themethods of synthesis described herein.

Synthesis of fluorinated compounds described herein in the absence oforganic solvents, in some embodiments, can facilitate the production ofaqueous dispersions of the fluorinated compounds. The absence of anorganic solvent, for example, can preclude the requirement to strip orfurther process the organic solvent during production of the aqueousdispersion. As a result, in some embodiments, water can be addeddirectly to the reaction mixture comprising a fluorinated compound toproduce an aqueous dispersion of the fluorinated compound. In someembodiments, water can be added directly to the reaction mixturecomprising a fluorinated compound to produce an aqueous dispersionhaving any of the weight percents of particles of fluorinated compoundsrecited herein.

In a further aspect, the present provides methods of enhancing the oiland/or water repellency of substrates, including fibers, textiles,carpets and floor coverings. In one embodiment, a method of enhancingthe oil and/or water repellency of a substrate comprises providing anaqueous dispersion of a fluorinated compound described herein andapplying the aqueous dispersion to the substrate.

In some embodiments, applying the aqueous dispersion to the substratecomprises spray coating, dip coating, foaming, exhausting, passing thesubstrate through kiss rollers or spreading onto or coating thesubstrate through a head box, optionally with the aid of a doctor bladeor any other application or exhaustion method or technique known to oneof skill in the art.

Some exemplary embodiments of the present invention will now beillustrated in the following specific, non-limiting examples.

Example 1 Synthesis of a Fluorinated Compound

A non-limiting embodiment of fluorinated compound of the presentinvention was produced according to the following method. 32.25 kg ofDESMODUR® N-3300A (165.44 NCO molar equivalent by titration) (BayerMaterials Science of Leverkusen, Germany) and 0.220 kg (2.07 mole) ofdiethylene glycol were provided to a reaction vessel. The agitator ofthe reaction vessel was set to 30 rpm and 0.018 kg of dibutyltin lauratecatalyst was added to the reaction vessel. The reaction vessel wasclosed and heated to a temperature of 95° C. for two hours with the headspace in the reaction vessel being swept by nitrogen.

14.99 kg (19.99 mol) of MPEG 750 and 52.54 kg of1H,1H,2H,2H-tridecafluoro-1-n-octanol (144.34 mol)(FLUOWET® EA-600 fromClariant GmbH) were added to the reaction mixture in the reactionvessel. The reaction vessel was heated to 95° C. for a period of twohours to produce the fluorinated compound. The reaction product wasanalyzed to verify the absence of unreacted isocyanate groups within thelimits of detection of the analytical methods used. The fluorinatedcompound produced by the foregoing method had a molecular weight ofabout 4,600.

Example 2 Production of an Aqueous Dispersion of a Fluorinated Compound

The reaction mixture comprising the fluorinated compound synthesized inExample 1 was diluted with a sufficient amount of water to produce anaqueous dispersion comprising particles of the fluorinated compound inan amount of about 30 weight percent. No dispersing aids were added toassist in producing the dispersion of the fluorinated compound ofExample 1. Moreover, as the fluorinated compound of Example 1 wasproduced without organic solvents, stripping of organic solvent from theaqueous dispersion was precluded.

Example 3 Synthesis of a Compound of Fluorinated Compound

A non-limiting embodiment of a fluorinated compound of the presentinvention was produced according to the following method. 9.74 kg ofDESMODUR® N-3300A (46.7 NCO molar equivalent by titration) (BayerMaterials Science of Leverkusen, Germany) and 0.066 kg (0.58 mole) ofdiethylene glycol were provided to a reaction vessel. The agitator ofthe reaction vessel was set to 30 rpm and 0.005 kg of dibutyltin lauratecatalyst was added to the reaction vessel. The reaction vessel wasclosed and heated to a temperature of 95° C. for two hours with the headspace in the reaction vessel being swept by nitrogen.

1.6 kg (11.64 mol) of 1,3-dichloro-2-propanol, 4.53 kg (5.64 mol) ofMPEG 750 and 11.45 kg of 1H,1H,2H,2H-tridecafluoro-1-n-octanol (29.4mol) (FLUOWET® EA-600 from Clariant GmbH) were added to the reactionmixture in the reaction vessel. The reaction vessel was heated to 95° C.for a period of two hours to produce the fluorinated compound. Thereaction product was analyzed to verify the absence of unreactedisocyanate groups within the limits of detection of the analyticalmethods used. The fluorinated compound produced by the foregoing methodhad a molecular weight of about 2,200.

Example 4 Production of an Aqueous Dispersion of a Fluorinated Compound

The reaction mixture comprising the fluorinated compound synthesized inExample 3 was diluted with a sufficient amount of water to produce anaqueous dispersion comprising particles of the fluorinated compound inan amount of about 27.4 weight percent. No dispersing aids were added toassist in producing the dispersion of the compound of Formula (I).Moreover, as the fluorinated compound of Example 3 was produced withoutorganic solvents, stripping of organic solvent from the aqueousdispersion was precluded.

Various embodiments of the invention have been described in fulfillmentof the various objectives of the invention. It should be recognized thatthese embodiments are merely illustrative of the principles of thepresent invention. Numerous modifications and adaptations thereof willbe readily apparent to those skilled in the art without departing fromthe spirit and scope of the invention.

Example 5 Synthesis of a Fluorinated Compound

A non-limiting embodiment of fluorinated compound of the presentinvention was produced according to the following method. 94.73 g ofDESMODUR® N-3300A (0.492 NCO molar equivalent by titration) (BayerMaterials Science of Leverkusen, Germany) and 0.05 g of dibutyltindilaurate catalyst were provided to a reaction glass vessel. Theagitator of the reaction vessel was set to 30 rpm, the batch was heatedto 50° C. and 3.6 g (0.006 mole) of polyethylene glycol (PEG) 600 wasadded to the reaction vessel. The reaction vessel was closed and heatedto a temperature of 65° C. for two hours with the head space in thereaction vessel being swept by nitrogen.

44.1 g (0.0588 mol) of MPEG 750 and 154.34 g of1H,1H,2H,2H-tridecafluoro-1-n-octanol (0.424 mol) (FLUOWET® EA-600 fromClariant GmbH) were added in three portions over two hours to thereaction mixture in the reaction vessel. The reaction vessel was heatedto 85° C. for a period of one hour after the last addition to producethe fluorinated compound. The reaction product was analyzed to verifythe absence of unreacted isocyanate groups within the limits ofdetection of the analytical methods used. The fluorinated compoundproduced by the foregoing method had a molecular weight of about 3,900.

Example 6 Synthesis of a Fluorinated Compound

A non-limiting embodiment of fluorinated compound in of the presentinvention was produced according to the following method. 94.73 g ofDESMODUR® N-3300A (0.492 NCO molar equivalent by titration) (BayerMaterials Science of Leverkusen, Germany) and 0.05 g of dibutyltindilaurate catalyst were provided to a reaction glass vessel. Theagitator of the reaction vessel was set to 30 rpm, the batch was heatedto 50° C. and 7.2 g (0.012 mole) of polyethylene glycol (PEG) 600 wasadded to the reaction vessel. The reaction vessel was closed and heatedto a temperature of 65° C. for two hours with the head space in thereaction vessel being swept by nitrogen.

39.63 g (0.0528 mol) of MPEG 750 and 152.154 g of1H,1H,2H,2H-tridecafluoro-1-n-octanol (0.418 mol) (FLUOWET® EA-600 fromClariant GmbH) were added in three portions over two hours to thereaction mixture in the reaction vessel. The reaction vessel was heatedto 85° C. for a period of one hour after the last addition to producethe fluorinated compound. The reaction product was analyzed to verifythe absence of unreacted isocyanate groups within the limits ofdetection of the analytical methods used. The fluorinated compoundproduced by the foregoing method had a molecular weight of about 4,500.

Various embodiments of the invention have been described in fulfillmentof the various objectives of the invention. It should be recognized thatthese embodiments are merely illustrative of the principles of thepresent invention. Numerous modifications and adaptations thereof willbe readily apparent to those of skill in the art without departing fromthe spirit and scope of the invention.

That which is claimed is:
 1. A fluorinated compound of Formula (I):

wherein Z is a trivalent organic group; L is a residue of a divalentdiol, a diamine, a urea, a dialcohol amine, an aminoalcohol or a mixturethereof; n ranges from 1 to 30; and A¹, A², A³ and A⁴ are independentlyselected from R^(f)—R^(a)—X—; and R^(o)—X—, wherein at least one of A¹,A², A³ and A⁴ is R^(f)—R^(a)—X— and at least one of A¹, A², A³ and A⁴ isR^(o)—X—, wherein R^(f) is a fluoroalkyl; R^(a) is a direct bond, analkyl, —C_(m)H_(2m)SO—, —C_(m)H_(2m)SO₂—, —SO₂N(R¹)—, or —CON(R¹)—,wherein m ranges from 1 to 20 and R¹ is hydrogen or an alkyl; X is —O—,—S— or —N(R²)—, wherein R² is hydrogen or alkyl; and R^(o) is methyl,ethyl, propyl, chlorinated methyl, chlorinated ethyl, chlorinatedpropyl, —R³—O—R⁴,

or —O—C(O)—R²⁵, wherein R³, R⁴, R⁵, R⁶, R²⁴ and R²⁵ are independentlyselected from the group consisting of methyl, ethyl, and propyl, and pranges from 1 to
 50. 2. The compound of claim 1, wherein L is a residueof a divalent diol comprising ethylene glycol; diethylene glycol;triethylene glycol; tetraethylene glycol; propylene glycol; dipropyleneglycol; tripropylene glycol; 1,3-propanediol; 1,3-butanediol;1,4-butanediol; neopentyl glycol; 1,6-hexanediol; 1,4-cyclohexanediol;or a mixture thereof.
 3. The fluorinated compound of claim 2, wherein Zcomprises one or more of


4. The fluorinated compound of claim 2, wherein R^(f)—R^(a)—X— comprisesa residue having the formula (C_(q)F_(2q+1))(CH₂)_(u)O—, wherein qranges from 4 to 20, and wherein u ranges from 1 to
 20. 5. Thefluorinated compound of claim 4, wherein R^(f)—R^(a)—X— comprises(C₄F₉)(CH₂)_(u)O—, (C₆F₁₃)(CH₂)_(u)O—, (C₈F₁₇)(CH₂)_(u)O—,(C₁₀F₂₁)(CH₂)_(u)O—, (C₁₂F₂₅)(CH₂)_(u)O—, 3(C₁₄F₂₈)(CH₂)_(u)O—,(C₁₆F₃₃)(CH₂)_(u)O—, (C₁₈F₃₉)(CH₂)_(u)O—, or (C₂₀F₄₁)(CH₂)_(u)O—, ormixtures thereof.
 6. The compound of claim 2, wherein R^(o)—X— comprisesa residue of a monoalkyl ether of a polyethylene glycol or a monoalkylether of a polypropylene glycol.
 7. The fluorinated compound of claim 2,wherein R^(o)—X— comprises a residue of a chlorinated alcohol.
 8. Thefluorinated compound of claim 7, wherein the chlorinated alcoholcomprises 1,3-dichloro-2-propanol, 2,2,2-trichloroethanol or2,2-dichloroethanol or mixtures thereof.
 9. The fluorinated compound ofclaim 2, wherein R^(o) is

and R⁵ and R⁶ independently are methyl, ethyl, or propyl.
 10. Thefluorinated compound of claim 9, wherein R⁵ is ethyl and R⁶ is methyl.11. The fluorinated compound of claim 10, wherein p ranges from about 7to about
 33. 12. The fluorinated compound of claim 2, wherein thecompound has a molecular weight ranging from about 8,250 to about20,000.
 13. The fluorinated compound of claim 1, wherein L comprises aresidue of a diamine, a dialcohol amine, or an aminoalcohol.
 14. Thefluorinated compound of claim 13, wherein L is selected fromethylenediamine, propylene diamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, urea, diethanolamine,methyldiethanolamine, phenyldiethanolamine, or a mixture thereof. 15.The fluorinated compound of claim 13, wherein R^(f)—R^(a)—X— comprises aresidue having the formula (C_(q)F_(2q+1))(CH₂)_(u)O—, wherein q rangesfrom 4 to 20 and u ranges from 1 to
 20. 16. The compound of claim 13,wherein R^(o)—X— comprises a residue of a monoalkyl ether of apolyethylene glycol or a monoalkyl ether of a polypropylene glycol. 17.The fluorinated compound of claim 13, wherein R^(o)—X— comprises aresidue of a chlorinated alcohol.
 18. The fluorinated compound of claim13, wherein R^(o) is

and R⁵ and R⁶ independently are methyl, ethyl, or propyl, and wherein pranges from about 7 to about
 33. 19. The fluorinated compound of claim13, wherein the compound has a molecular weight ranging from about 8,250to about 20,000.
 20. A fluorinated compound of Formula (I):

wherein Z comprises one or more of

L is a residue of a divalent diol comprising ethylene glycol; diethyleneglycol; triethylene glycol; tetraethylene glycol; propylene glycol;dipropylene glycol; tripropylene glycol; 1,3-propanediol;1,3-butanediol; 1,4-butanediol; neopentyl glycol; 1,6-hexanediol;1,4-cyclohexanediol; or a mixture thereof; n ranges from 1 to 30; andA¹, A², A³ and A⁴ are independently selected from R^(f)—R^(a)—X—; andR^(o)—X—, wherein at least one of A¹, A², A³ and A⁴ is R^(f)—R^(a)—X—and at least one of A¹, A², A³ and A⁴ is R^(o)—X—, wherein R^(f) is afluoroalkyl; IV is a direct bond, an alkyl, —C_(m)H_(2m)SO—,—C_(m)H_(2m)SO₂—, —SO₂N(R¹)—, or —CON(R¹)—, wherein m ranges from 1 to20 and R¹ is hydrogen or an alkyl; X is —O—, —S— or —N(R²)—, wherein R²is hydrogen or alkyl; and R^(o) is methyl, ethyl, propyl, chlorinatedmethyl, chlorinated ethyl, chlorinated propyl, —R³—O—R⁴,

—O—R²⁴—O—C(O)—R²⁵, or wherein R³, R⁴, R⁵, R⁶, R²⁴ and R²⁵ areindependently selected from the group consisting of methyl, ethyl, andpropyl, and p ranges from 1 to 50; and wherein the compound has amolecular weight ranging from about 8,250 to about 20,000.